JPH0247736B2 - HAROGENKAGINSHASHINKANKOZAIRYONOSHORIHOHO - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for processing a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a novel cyan dye image-forming coupler. Normally, color images are produced by an aromatic primary amine color developing agent reducing exposed silver halide grains, forming oxidation products of the color developing agent and yellow, magenta, and cyan dyes. A coupler is formed by oxidative coupling in a silver halide emulsion. Couplers typically used to form cyan dyes are phenols and naphthols. Considering the photographic performance of conventional couplers, especially for phenols, the basic properties required are that the dye has good spectral absorption characteristics, that is, it has no absorption in the green region of the spectrum and is sharp, and that the formed dye is sensitive to light. It goes without saying that silver halide photographic materials must have sufficient fastness against heat, moisture, etc., and have good color development, that is, sufficient color development sensitivity and color density. It has been a long-standing aspiration to speed up the series of steps in which images are obtained by development after imagewise exposure. As one means for solving this demand, a technique is known in which a bleach-fixing process is performed in which a bleaching process and a fixing process are performed simultaneously. On the other hand, in recent years, aminopolycarboxylic acid metal complex salts (e.g.
A common method is to use EDTA (ferric salt) in the bleach-fixing process, but if you get tired from running,
There is a problem in that the dyes forming the image are likely to be lost (especially cyan dyes). Therefore, there is a strong demand that, for example, bleach-fix baths containing EDTA ferric salt as a main component do not lose color even when fatigued by running. Furthermore, from the viewpoint of depollution, the removal of benzyl alcohol added to color developing solutions has been taken up as a major problem. However, the current situation is that sufficient color development cannot generally be obtained unless benzyl alcohol is added. The decrease in color development due to the removal of benzyl alcohol is particularly noticeable in phenolic cyan couplers, and from this point of view as well, there is a demand for phenolic cyan couplers that exhibit high color development even without benzyl alcohol. Research has been carried out to satisfy the above requirements, but to the best of the knowledge of the present inventors, a cyan coupler that satisfies all of the above required properties has not yet been found. For example, 6-[α-(2,4-di-t-amylphenoxy)butanamide]-2,4-dichloro-3-methylphenol described in U.S. Patent No. 2801171 has good light resistance but heat resistance. In addition to having disadvantages in terms of performance, there is also a large loss of dye in a tired bleach-fix solution. Furthermore, color development is highly dependent on benzyl alcohol, and it is difficult to remove benzyl alcohol from the color developing solution. US Patent No.
2-Heptafluorobutanamide-5-[α-(2,4-di-t-amylphenoxy)hexanamide]phenol described in No. 2895826 has excellent heat resistance and dye loss in a tired bleach-fix bath. However, it is inferior in terms of light resistance and color development. Furthermore, the coupler described in JP-A-53-109630 also has problems in terms of removal of benzyl alcohol and light resistance. Additionally, U.S. Patent No.
No. 3839044, Japanese Patent Application Publication No. 1983-37425, Publication No. 37425, Publication No. 1973-
Publication No. 36894, Japanese Unexamined Patent Publication No. 50-10135, Japanese Patent Publication No. 50-117422
No. 50-130441, No. 50-108841, No. 50-
The phenolic cyan couplers described in Publication No. 120334 and the like are also unsatisfactory in terms of heat resistance and removal of benzyl alcohol. Phenolic couplers having a ureido group at the 2-position are described in British Patent No. 1011940 and US Patent Nos. 3446622, 3996253, and
As described in No. 3758308 and No. 3880661, etc., the cyan dyes formed by these couplers have broad spectral absorption, and furthermore, the absorption maximum is in the relatively short wave region of the red region, so they are suitable for the green region of the spectrum. It has considerable absorption and is unfavorable in terms of color reproduction. Although the phenolic coupler having a ureido group at the 2-position described in JP-A-56-65134 has considerably improved green absorption in the spectral region,
Other characteristics are still insufficient. Therefore, an object of the present invention is to provide a method for processing silver halide photographic materials, which speeds up the processing of silver halide photographic materials, and which does not cause loss of cyan dye even when the processing solution is subjected to running processing. Our goal is to provide the following. As a result of extensive research into these conventional techniques, the present inventors have found that the 2-position substitution,
or a fused-4-cyanophenylureido group,
A silver halide emulsion layer containing a phenolic cyan coupler having a hydrogen atom or a group that can be eliminated by coupling with an oxidation product of a color developing agent at the 4-position and a ballasted acylamino group at the 5-position. By employing a processing method for silver halide photographic materials that includes the following steps: (i) imagewise exposure, (ii) color development, and (iii) bleach-fixing, photographic materials can be processed to achieve the desired objectives. was able to achieve this. The substituent of the substituted-4-cyanophenylureido group is of course located on the phenyl group, but preferably has the following general formula. [In the formula, Y is an alkyl group, preferably C ₁ to _{C 5}
branched or straight-chain alkyl groups, halogens such as chlorine and bromine, hydroxyl groups, nitro groups, _C1 - _C5 aliphatic groups, acyloxy groups (preferably aromatic acyloxy groups), alkoxy groups (preferably _C1 -C5 ₅ ), an acyl group (aromatic acyl group, aliphatic acyl group), and m represents an integer of 1 to 4. Note that when m≧2, Y may be the same or different. The fused-4-cyanophenyl ureido group forms a ring at the 2- and 3-positions of the phenyl moiety, and is preferably expressed by the following general formula. In the formula, Y is the same as defined above and may be present in the phenyl moiety or the Z moiety. n is 0~
Represents an integer of 4. Z represents a group of nonmetallic atoms that together with the benzene ring form a 5- or 6-membered condensed ring. Examples of the condensed ring formed with Z include naphthalene, quinoline, benzothiophene, benzofuran, and isocoumaran. Specific examples of groups that can be released in a coupling reaction include halogen atoms (e.g., chlorine, bromine, fluorine, etc.), aryloxy groups in which an oxygen or nitrogen atom is directly bonded to the coupling position, and carbamoyl Oxy group, carbamoylmethoxy group, acyloxy group, sulfonamide group,
Examples include succinimide groups, and more specific examples include U.S. Pat.
No. 37425, Special Publication No. 1974-36894, Japanese Patent Publication No. 10135, No. 1973
No. 50-117422, No. 50-130441, No. 51-
No. 108841, No. 50-120334, No. 52-18315, No.
Those described in publications such as No. 53-52423 and No. 53-105226 are useful. Ballasted acylamino group ballasts act as "weights" in multilayer color photographic elements to hold couplers in a particular layer and substantially prevent diffusion to other layers; “Bulk” is necessary. Specific examples of acylamino include aromatic acylamino and aliphatic acylamino, but in the case of aromatic acylamino, the aromatic ring requires a substituent having a C ₅ -C ₁₈ alkyl chain. Examples of the substituent having a _C5 to _C18 alkyl chain include an alkyl group, an acyloxy group, an acylamino group, a sulfonylamino group,
Examples include an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylamino group, and a dialkylamino group. In the case of aliphatic acylamino, typical examples of the aliphatic group include a _C5 to _C18 long chain alkyl group, furthermore, a phenoxyalkyl group and a phenylthioalkyl group. In the case of phenoxyalkyl groups and phenylthioalkyl groups, there are cases where the phenoxy moiety has a substituent having a C5 to C18 alkyl chain, and cases where the alkyl moiety itself has a substituent having a _C5 to _C18 alkyl chain.
It may have _C5 to _C18 carbon. As the ballasted acylamino group of the present invention, particularly a phenoxyalkyl group or a phenylthioalkyl group gives preferable results. Specific examples of acylaminos that ballast phenoxyalkyl groups include the following. α-(3-pentadecylphenoxy)butanamide α-(2,4-di-t-amylphenoxy)hexanamide γ-(2,4-di-t-amylphenoxy)butanamide α-(2,4-di- t-amylphenoxy)tetradecanamide α-(4-butylsulfonylaminophenoxy)tetradecanamide α-(4-butylsulfamoylphenoxy)
Tetradecanamide α-(4-acetoxyphenoxy)dodecanamide α-{p-[α-(4-hydroxyphenyl)
-α,α-dimethyl]tolyloxy}dodecanamide α-(4-carboxyphenoxy)dodecanamide α-(2-chloro-4-butylsulfonylaminophenoxy)tetradecanamide α-(4-dimethylaminosulfonyl aminophenoxy)tetradecanamide α-(3-dodecyloxyphenoxy)butanamide α-(4-dodecyloxyphenoxy)butanamide α-(4-hydroxyphenylthio)dodecanamide α-(4-acetylamino Phenylthio)dodecaneamide Specific compound examples of the phenolic cyan coupler of the present invention are illustrated below, but the invention is not limited thereto. The phenolic cyan couplers of the present invention are prepared by reacting a substituted p-cyanophenyl isocyanate with a suitable aminophenol, such as 2-amino-5-nitrophenol or 2-amino-4-chloro-5-nitrophenol. 2-(substitution-p-
It can be produced by producing a cyanophenyl)ureido compound. It can then be obtained by reducing the nitro group to an amine by a conventional method and bonding the ballast group to the amine. Typical synthesis examples of the phenolic cyan coupler of the present invention are shown below. Synthesis Example 1 (Exemplary Coupler 2) (a) 2-(p-cyano-m-methoxyphenyl)
Synthesis of ureido-5-nitrophenol 15.4g of 2-amino-5-nitrophenol
Suspend in 300ml of toluene and reflux. to this
A solution of 17.4 g of p-cyano-m-methoxyphenyl isocyanate in 150 ml of toluene was added dropwise with stirring. After the dropwise addition, the reaction solution was heated under reflux for 1 hour, and then cooled. The precipitate was filtered and washed with hot toluene and then alcohol to obtain 1.22 g of the desired product. (a) Synthesis of Exemplary Coupler 2 Using 6.6 g of 2-(p-cyano-m-methoxyphenyl)ureido-5-nitrophenol and a palladium-carbon catalyst, in 200 ml of alcohol,
The hydrogenation reaction was carried out at room temperature and pressure. Next, palladium-carbon was removed by filtration, the filtrate was concentrated, and the residue was reduced to 200ml.
of acetonitrile. To this was added 1.6 g of pyridine, and further 9.5 g of 2-(4-butylsulfonylaminophenoxy)tetradecanoyl chloride was added at room temperature with stirring. After stirring at room temperature for 5 hours, the mixture was poured into water and extracted with ethyl acetate. Ethyl acetate was distilled off, and the residue was recrystallized from methanol and further from acetonitrile to obtain 7.2 g of the desired product. The target product was confirmed by mass spectroscopy and nuclear magnetic resonance spectroscopy. Synthesis Example 2 (Exemplary Coupler 1) (A) Synthesis of 2-(0-chloro-p-cyanophenyl)ureido-4-chloro-5-nitrophenol 18.8 g of 2-amino-4-chloro-5-nitrophenol, 27.3g phenyl O-chloro-p-
Cyanophenyl carbamate and 0.68 g of imidazole were heated to reflux in 400 ml of xylene for 5 hours. After cooling, the precipitate was filtered and washed with xylene and a small amount of alcohol to obtain 23.5 g of the desired product. (a) Synthesis of Exemplary Coupler 1 Using 11 g of 2-(O-chloro-p-cyanophenyl)ureido-4-chloro-5-nitrophenol and a palladium-carbon catalyst, in 300 ml of alcohol at room temperature and pressure. Catalytic reduction with hydrogen was carried out. After the reaction, the catalyst was filtered off, the filtrate was concentrated, and 250 ml of acetonitrile was added to the residue. to this
Add 2.4g of pyridine and add 12.3g of 2-(3) at room temperature.
-pentadecylphenoxy)butanoyl chloride was added with stirring. After stirring at room temperature for 6 hours, the mixture was poured into water and extracted with ethyl acetate. The residue obtained by distilling off ethyl acetate was subjected to chromatography using silica gel as a carrier and benzene-ethyl acetate as an eluent. The target product fractions were combined and the solvent was distilled off. The residue was further crystallized from methanol.
5.8g of the target product was obtained. The target product was confirmed using mass spectra and nuclear magnetic resonance spectra. For the cyan dye-forming coupler used in the present invention (hereinafter referred to as "the coupler according to the present invention"), the method techniques used for ordinary cyan dye-forming couplers can be similarly applied. Typically, a coupler is incorporated into a silver halide emulsion and this emulsion is coated onto a base to form a silver halide photographic material. Silver halide photographic materials (photographic elements) can be single color elements or multicolor elements. In multicolor elements, the phenolic cyan couplers of this invention are typically included in red-sensitive emulsions, but
They may be included in unsensitized emulsions or dye image-forming units sensitive to each of the three primary color regions of the spectrum. Each structural unit can consist of a single emulsion layer or multiple emulsion layers that are sensitive to a certain region of the spectrum. The layers of the element, including the amount of imaging units, can be arranged in various orders as is known in the art. A typical multicolor photographic element consists of a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler (at least one of the cyan dye-forming couplers is according to the present invention). a phenolic cyan coupler), a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer having at least one magenta dye-forming coupler and at least one blue having at least one yellow dye-forming coupler. It consists of a yellow dye image-forming structural unit consisting of a sensitive silver halide emulsion layer supported on a base. The element can have additional layers such as filter layers, interlayers, protective layers, subbing layers, etc. In order to incorporate the phenolic cyan coupler according to the present invention into an emulsion, a conventionally known method may be followed. For example, the phenol of the present invention may be added to a high boiling point organic solvent with a boiling point of 175°C or higher such as tricresyl phosphate or dibutyl phthalate, or a low boiling point solvent such as butyl acetate or butyl propionate, or in a mixture thereof as necessary. After dissolving the based cyan couplers alone or in combination, mixing with an aqueous gelatin solution containing a surfactant, and then emulsifying with a high-speed rotating mixer or colloid mill,
The silver halide emulsion used in the present invention can be prepared by adding it to silver halide. When the phenolic cyan coupler according to the present invention is added to the silver halide emulsion of the present invention, it is usually added in an amount of about 0.07 to 0.7 mol, preferably 0.1 mol to 0.4 mol, per 1 mol of silver halide. Such a phenolic cyan coupler is added. The silver halide used in the silver halide emulsion of the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc., which are commonly used in silver halide emulsions. Anything is included. The silver halide emulsion constituting the silver halide emulsion of the present invention can be manufactured by various manufacturing methods including the usual manufacturing method, for example, the method described in Japanese Patent Publication No. 46-7772, i.e., the solubility is higher than that of silver bromide. big,
A method of manufacturing a so-called conversion emulsion, such as forming an emulsion of silver salt grains consisting of at least a portion of silver salt, and then converting at least a portion of the grains to silver bromide or silver iodobromide salt, or a method of manufacturing a so-called conversion emulsion, or a method of manufacturing a silver salt grain of 0.1μ or less. It can be produced by any production method such as the Lipman emulsion production method consisting of fine-grained silver halide having an average grain size of . Furthermore, the silver halide emulsion of the present invention may contain sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers such as stannous salts, polyamines, etc. etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-oresulfobenzthiazole methyl chloride, etc., or water-soluble salts such as ruthenium, rhodium, iridium, etc. Sensitizers, specifically ammonium chloroparadate,
Chemical sensitization can be carried out using potassium chloroplatinate, sodium chloroparadide, etc. alone or in appropriate combination. Furthermore, the silver halide emulsion of the present invention can contain various known photographic additives. For example, photographic additives such as those described in Research Disclosure. December 1978 Item 17643. The silver halide of the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the wavelength range required for red-sensitive emulsions. Various spectral sensitizing dyes are used, and these can be used alone or in combination of two or more.
Spectral sensitizing dyes that can be advantageously used in the present invention include, for example, US Pat. No. 2,269,234;
Typical examples include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in the specifications of No. 2270378, No. 2442710, No. 2454629, and No. 2776280. The color developing solution that can be used in the present invention preferably has an aromatic primary amine color developing agent as a main component. Typical examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, and dimethyl-p-phenylenediamine hydrochloride. Diamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-
dodecylamino)-toluene, 2-amino-5-
(N-ethyl-N-β-methanesulfonamidoethyl)aminotoluene sulfate, 4-(N-ethyl-N-β-methanesulfonamidoethylamino)
Aniline, 4-(N-ethyl-N-β-hydroxydiethylamino)aniline, 2-amino-5-
Examples include (N-ethyl-N-β-methoxyethyl)aminotoluene. After development, bleach-fixing is carried out to remove silver and silver halide, and if necessary, usual steps of washing and drying are carried out. Next, preferred embodiments of the present invention will be listed. (1) A method for processing a silver halide photographic material according to the claims, in which the substituted-4-cyanophenylureido group has the following general formula. (In the formula, Y represents an alkyl group, halogen, hydroxyl group, nitro group, acyloxy group, alkoxy group, or acyl group, and m represents an integer of 1 to 4. When m2, Y may be the same or (2) A method for processing a silver halide photographic light-sensitive material according to the claims, in which the condensed-4-cyanophenyl ureido group has the following general formula. (In the formula, Y is the same as defined above, and may be present in the phenyl moiety or the Z moiety.
n represents an integer from 0 to 4. Z represents a group of nonmetallic atoms that together with the benzene ring form a 5- or 6-membered condensed ring. ) The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto. Examples (1) Phenolic cyan couplers according to the present invention as shown in Table 1 and comparative couplers [A] below,
0.03 moles of each of [B] and [C] were added to a mixed solution containing the same amount of dibutyl phthalate and three times the amount of ethyl acetate, and the mixture was heated to 60° C. to completely dissolve. This solution was added to an aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and gelatin, and emulsified using a colloid mill to prepare respective coupler dispersions. Next, this coupler dispersion was added to a silver chlorobromide emulsion containing 0.1 mol of silver (20 mol% silver bromide), coated on polyethylene laminate paper, and dried to form six types of silver with stable coating films. Silver halide photographic materials (sample numbers [1] to [6]) were obtained. These samples were subjected to wedge exposure according to a conventional method and then subjected to the following processing. However, the color development process was carried out for two types of compositions: one with benzyl alcohol added (color development [1]) and one without (color development [2]). [Processing] Processing step (30°C) Processing time Color development 3 minutes 30 seconds Bleach-fixing 1 minute 30 seconds Water washing 2 minutes The composition of each treatment is shown below. [Color developer composition 1] [4-Amino-3-methyl-N-ethyl-N-
(β-Methanesulfonamidoethyl)-Aniline sulfate 5.0g Benzyl alcohol 15.0ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.85g Sodium bromide 1.4g Potassium bromide 0.5g Borax 39.1g Add water to make 1, then water Adjust the pH to 10.30 using sodium oxide. ] [Color developer composition 2] [4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 5.0g Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.85g Sodium bromide 1.4g Potassium bromide 0.5g Borax 39.1g Add water to make 1, and use sodium hydroxide. and adjust the pH to 10.30. ] [Bleach-fix solution composition] [Ethylenediaminetetraacetic acid iron ammonium salt 50g Ammonium sulfite (40% solution) 50ml Ammonium thiosulfate (70% solution) 140ml Aqueous ammonia (28% solution) 20ml Ethylenediaminetetraacetic acid 4g Add water to make 1 . ] The photographic characteristics of each of the obtained samples were measured. The results are shown in Table 1. The relative sensitivity values in the table are expressed with the maximum sensitivity value when processed with color developer [1] being 100.

[Table] As is clear from Table 1 above, samples containing the phenolic cyan coupler according to the present invention were subjected to bleach-fixing treatment, and both color development with benzyl alcohol and color development without benzyl alcohol were good. It can be seen that the sensitivity and maximum density are excellent. In addition, as a result of measuring the color spectrum, the dye using the phenolic cyan coupler according to the present invention has a maximum absorption maximum in a relatively long part of the red region, and shows excellent color purity with little absorption on the short wavelength side. It turned out that. Example (2) Using a sample obtained in the same manner as in Example (1) above, the light resistance, heat resistance, and moisture resistance of the dye image were investigated. The results obtained are shown in Table 2.

[Bleach-fix solution composition]

[Ethylenediaminetetraacetic acid iron ammonium salt 50g Ammonium sulfite (40% solution) 50ml Ammonium thiosulfate (70% solution) 140ml Aqueous ammonia (28% solution) 20ml Ethylenediaminetetraacetic acid 4g Hydrosulfite 5g Add water to make 1. ] The maximum density of the cyan dye of the sample obtained through development processing was measured. The results are shown in Table 3. Incidentally, the dye residual rate at the maximum density portion was determined as follows. Dye residual rate = Fatigue bleach-fix solution treatment/new bleach-fix solution treatment x 100

【table】

[Table] From Table 3, it can be seen that the samples using the phenolic cyan coupler according to the present invention show less fading of the cyan dye even when treated with a fatigued bleach-fix solution.

Claims (1)

[Scope of Claims] 1. A substituted or condensed 4-cyanophenylureido group at the 2-position on the support, a hydrogen atom at the 4-position, or a group that can be separated by coupling with an oxidation product of a color developing agent, 5. A silver halide photographic light-sensitive material having a silver halide emulsion layer containing a phenolic cyan coupler having an acylamino group ballasted at position is processed by the following steps: (i) imagewise exposure (ii) color development (iii) ) A method for processing a silver halide photographic material, including each step of bleach-fixing processing.